EP1475073A2 - Hair cosmetic cleaning composition with active compound combinations consisting of gamma oryzanol and calcium salts with a low metal ion concentration - Google Patents

Abstract

A hair cleansing composition contains gamma-oryzanol and one or more calcium salts selected from calcium pantothenate, calcium chloride and calcium lactate. The concentration of free polyvalent metal ions is less than 0.004 M.

Description

The present invention relates to cosmetic active ingredient combinations and preparations, containing such active ingredient combinations. In particular, the present concerns Invention hair cosmetic cleaning preparations or hair cosmetic Detergent containing substances that damage the scalp and / or hair, but also protect the preparations themselves against undesired oxidation processes. In a preferred embodiment, the present invention relates to active ingredient combinations and preparations with it, which serve to close the hair and scalp care for.

Oxidative processes damage substances of all kinds (e.g. skin, hair and Wool, but also varnishes and plastics, just to name a few) partly in considerable measure. The substances change their physical and chemical Properties: they "age". To delay or even inhibit the aging of So-called anti-aging agents are generally used.

In particular, the damaging effect of the ultraviolet part of solar radiation Organic, but also inorganic substances are generally known. For the people are the damage to the skin and hair and the delay or Prevention of the same through the use of light stabilizers of special Importance.

The whole human body except the lips, palms and the soles of the feet are hairy, but mostly with barely visible wool hairs. Because of the many nerve endings at the hair root, hair is sensitive to it external influences such as wind or touch and are therefore not a too underestimating part of the sense of touch. The main function of the human Today, however, scalp hair is likely to consist in the appearance of humans characteristic to help shape. Similar to the skin, it fulfills a social Function, as it is about interpersonal considerably about its appearance Relationships and contributes to the individual's self-esteem.

The hair consists of the hair shaft protruding freely from the skin - the keratinized (dead) part that represents the actually visible hair - and that in the skin stuck hair root - the living part in which the visible hair is constantly new is formed. The hair shaft itself is made up of three layers: one central part - the so-called hair mark (medulla), which, however, in humans is regressed and often completely missing - furthermore the marrow (cortex) and the outer cuticle layer (cuticle) up to ten layers thick that covers the entire hair envelops.

Unless there are pathological changes, human hair is in practically impossible to improve its freshly grown state. The Indian Part of a hair located near the scalp accordingly has an almost closed cuticle layer. In particular the cuticle layer as the outer shell of the hair, but also the inner area below the cuticle are particularly stressful exposed to environmental influences.

Significant influences for the loss of quality of a hair during its aging are the influence of sunlight, mechanical stress due to intensive combing or brushes, but also hair treatments, such as hair coloring and in particular Bleaching and hair shaping, for example permanent wave procedures. Especially Oxidative loads therefore often damage the hair.

Both UV-A and UV-B radiation have a damaging effect on that Hair, which is expressed, for example, in the fact that certain amino acids such as cystine and Degraded methionine or cleaved sulfur-sulfur bonds of keratin worst case, which can result in the destruction of the hair. Furthermore, hair and scalp represent parts of the body due to their position are exposed to a significant amount of UV radiation when outdoors.

With particularly aggressive stress, for example bleaching with oxidants like hydrogen peroxide, in which the pigments distributed in the cortex are oxidatively destroyed the inside of the hair can also be affected. Should human hair are permanently colored, in practice only oxidizing Hair coloring process into consideration. Training takes place in oxidative hair dyeing of the dye chromophore through reaction of precursors (phenols, aminophenols, less often diamines) and bases (mostly p-phenylenediamine) with the oxidizing agent, mostly hydrogen peroxide. Hydrogen peroxide concentrations are usually used used by 6%.

It is usually assumed that in addition to the coloring effect, there is also a bleaching effect done by the hydrogen peroxide. In oxidatively dyed human hair similar to bleached hair, there are microscopic holes in the areas which were present with melanin granules. The fact is that the oxidizer Hydrogen peroxide not only with the color precursors, but also with the hair substance reacts and may cause damage to the hair.

Oxidative influences, such as chemical hair treatments or sunlight, therefore reduce the strength and elasticity of the hair and lead to one Destruction of melanin. This is particularly evident in dark-haired People whose hair is significantly lightened in summer by intense sunlight becomes. Under the term "oxidative influence" is in the sense of the present invention to understand both the influence of oxidizing substances and the oxidative effect of radiation, especially light, especially UV light, resulting secondary products.

One goal of hair care is to protect the scalp and hair from oxidative influences and the natural state of freshly regrown hair as possible long period of time and to restore it in case of loss. silky Shine, low porosity and a pleasant, smooth feeling are characteristics of natural, healthy hair.

Products for hair care have been targeted since the end of the last century developed. This led to a variety of preparations for both general hair care as well as to fix hair and scalp abnormalities. in the general hair care cosmetics are used nowadays, which either are intended to be rinsed out of the hair after exposure, or which should remain on the hair. The latter can be formulated in such a way that they not only serve the care of the individual hair, but also the appearance of a Improve overall hairstyle, for example by giving the hair more body, fix the hairstyle over a longer period of time or improve the manageability.

The use of antioxidants, i.e. substances that cause oxidation processes prevent in cosmetics is known per se. Antioxidants used in cosmetics find, for example, tocopherols, bile acid derivatives, sesamol and Flavonoids. Antioxidants are mainly used as protective substances against the Spoilage of the preparations containing them.

Tocopherols, especially vitamin E, are of course also suitable in principle, oxidation processes to prevent, and accordingly often found in cosmetics Use. However, tocopherols have the disadvantage that they are generally very are reactive and therefore partially react already in the preparation. This leads to, that only a small part of the amount used is the part of the body to be protected at all achieved so that the effect achieved falls far short of the hoped for.

From EP-A-0706366 shampoo compositions are known, the one Concentration of 0.004 M to 0.08 M of polyvalent metal cations in free have ionic shape. As in the following, the "M" indicates the molarity.

Cosmetic preparations of this type, however, have the disadvantage of being influenced of light and / or warmth or after long storage in their appearance and / or to be able to change the smell disadvantageously because of their concentration of free polyvalent metal cations is too high.

An object of the present invention was to overcome the disadvantages of the prior art to eliminate. In particular, cosmetic active ingredients or preparations, such Containing active ingredients are made available, the use of which Damage to the scalp and / or hair reduced by oxidative influence, if it cannot be completely prevented. These cosmetic active ingredients or Preparations should be effective and cosmetic in appearance via a remain stable for a longer period.

According to the invention this object is achieved and the disadvantages of the prior art Technology eliminated.

The invention relates to hair cosmetic cleaning agents, thereby characterized in that they contain gamma-oryzanol and one or more calcium salts Calcium salts selected from the group formed by calcium panthotenate, Calcium chloride or calcium lactate, containing the concentration of in free Polyvalent metal cations present in ionic form is less than 0.004 M.

The invention particularly relates to hair cosmetic cleaning agents, characterized in that they contain gamma-oryzanol and one or more calcium salts Calcium salts selected from the group formed by calcium panthotenate, Calcium chloride and calcium lactate, and contain at least one complexing agent.

The invention also relates to combinations of active ingredients for hair cosmetics, thereby characterized in that they contain γ oryzanol and one or more calcium salts, selected from the group formed by calcium panthotenate, calcium chloride and Calcium lactate, and contain at least one complexing agent.

The invention furthermore relates to the use of active substance combinations and hair cosmetic detergents containing them, consisting of gamma-oryzanol and a calcium salt or more calcium salts selected from the Group formed from calcium panthotenate, calcium chloride and calcium lactate, the Concentration of polyvalent metal cations present in free ion form less is as 0.004 M, for the protection of hair cosmetic preparations and / or Scalp and / or hair before undesirable oxidation processes.

The invention furthermore relates to the use of active substance combinations and hair cosmetic detergents containing them, consisting of gamma-oryzanol and a calcium salt or more calcium salts selected from the Group formed by calcium panthotenate, calcium chloride and calcium lactate, and at least one complexing agent for the protection of hair cosmetic preparations and / or the scalp and / or the hair before undesirable oxidation processes.

Preferred hair cosmetic preparations are shampoos, for example Conditioning aids, in particular also water-soluble conditioning aids may contain, such as described below.

The active substance combinations and preparations according to the invention, these active substance combinations containing, reduce damage to the scalp and / or hair due to oxidative influences better than active substances, active substance combinations and Preparations of the state of the art. In particular, they maintain through oxidative Stress damaged or damaged hair or prevent such damage. In particular, the complexing agents mask those which may be present in Concentrations above 0.004 M in the form of free ions present polyvalent Metal cations, e.g. Calcium ions or magnesium ions that are undesirable Changes in the appearance and smell of the active ingredient combinations and these containing preparations would lead. In the masked or complexed form Surprisingly, the metal ions mentioned do not lead to the ones described Disadvantages.

Gamma-oryzanol is described in the literature (CAS no .: 11042-64-1 or 12738-23-7). Gamma-oryzanol is not a uniform compound, but a mixture differently structured ferulic acid esters. Gamma-oryzanol mainly exists from the esters of ferulic acid with the triterpene alcohols cycloartenol and 24-methylenecylcloartenol. It also contains small amounts of esters with sterols, namely with camesterol, stigmasterol and β-sitosterol.

Gamma-oryzanol is commercially available, for example under the trade name Gamma-Oryzanol (supplier: Jan Dekker or Henry Lamotte, DE).

Preparations according to the invention advantageously contain 0.001 to 5.0% by weight of gamma-oryzanol, preferably 0.01 to 2.0% by weight, in each case based on the total weight of the Preparations.

Preparations according to the invention advantageously contain 0.001 to 0.05% by weight of a or more calcium salts, preferably 0.02 to 0.05 wt .-%, each based on the Total weight of the preparations.

Calcium lactate is preferred as the calcium salt. The calcium salts are on the market available.

All complexing agents which complex polyvalent metal cations are suitable and the concentration of free polyvalent or free ionic form Metal cations, especially calcium ions and / or magnesium ions, in the Lower preparations according to the invention, especially below the concentration of 0.004 M.

Ethylene bis (oxyethylene nitrilo) tetraacetic acid (EGTA), Preferred ethylenediaminetetraacetic acid or iminodisuccinic acid, or their salts, especially water soluble salts, e.g. the sodium salts or potassium salts, wherein one or more carboxylic acid groups may each be present in the salt form.

Furthermore, complexing agents can advantageously be selected from the group of the usual compounds be selected, e.g. by adding at least one substance from the group consisting of tartaric acid and its anions, citric acid and its anions, Aminopolycarboxylic acids and their anions (such as Nitrilotriacetic acid (NTA) and its anions, Hydroxyethylenediaminotriessigsäure (HOEDTA) and their anions, diethylene aminopentaacetic acid (DPTA) and their Anions, trans-1,2-diaminocyclohexanetetraacetic acid (CDTA) and their Anions) is selected.

It can be accepted, but this assumption is not yet in all details It could be confirmed that a portion of the theoretically in the preparations available polyvalent metal cations, for example calcium or Magnesium ions, in the form of the complex according to the invention with gamma-oryzanol is present and a further proportion of these metal cations according to the invention, in particular is masked by the complexing agent and the concentration polyvalent metal cations, which are in free ion form, is below 0.004 M.

The water used to prepare the preparations is preferred demineralized or fully desalinated (VES) or has only a low water hardness or low concentration of calcium ions or magnesium ions if tap water is used. In these cases in particular, the Concentration of free polyvalent metal cations with respect to the invention lower concentration of 0.004 M checked, for example by measurements with a cation sensitive electrode.

Corrections can always be made by the specialist in, if appropriate or necessary be made in a known manner, for example by an adapted and e.g. controlled, higher dosage of the complexing agent by such a measurement or a lower dosage if the use of a complexing agent should be necessary since a lower dosage of polyvalent, free metal cations, especially calcium ions, below the upper limit a concentration of 0.004 M and if necessary by measurement can be set and controlled.

Preparations according to the invention advantageously contain 0.02-2.00% by weight of one or several complexing agents, preferably 0.05-1.0% by weight, based in each case on the Total weight of the preparations.

The complexing agents are also known and are commercially available.

The concentration of polyvalent in the preparations according to the invention is Metal cations, especially calcium ions, which are in free ion form, for example 0.000001 M - 0.0039 M, preferably 0.00001 M - 0.0039 M, especially 0.0001 M - 0.0038 M.

The hair cosmetic detergents and preparations, the invention Combinations of active ingredients are topical preparations. These can be like be composed as usual and for the treatment and care of the scalp and / or the hair or as a sunscreen preparation. The are used Preparations according to the invention for cosmetics and hair cleaners applied to the scalp and hair in sufficient quantities.

Preparations in the sense of the present invention can advantageously be used as emulsions or solutions are available.

The agents according to the invention can, for example, as from squeeze bottles or Preparations that can be metered by a pump or spray device are present, however in particular in the form of an agent that can be applied from normal bottles and containers.

Preparations according to the invention advantageously contain, in addition to an effective content usual combinations of active ingredients, contents, additives and / or Excipients.

Preparations according to the invention, the hair cosmetic cleaning preparations for representing the hair or scalp can be in liquid or solid form. They preferably contain at least one anionic, non-ionic or amphoteric surface-active substance or mixtures thereof, optionally an electrolyte and aids, as are usually used for this. The surface active Substance can be in a concentration between 1 and 94 wt .-% in the cleaning preparations are present, based on the total weight of the preparations, but especially between 1 and 50 wt .-%.

In particular, aqueous cosmetic cleaning agents or Low-water or water-free cleaning agent concentrates intended for aqueous cleaning contain anionic, nonionic and / or amphoteric surfactants, for example conventional soaps, e.g. Fatty acid salts of sodium, alkyl sulfates, Alkyl ether sulfates, alkane and alkyl benzene sulfonates, sulfoacetates, sulfobetaines, Sarcosinates, amidosulfobetaines, sulfosuccinates, sulfosuccinic acid semiesters, Alkyl ether carboxylates, protein fatty acid condensates, alkyl betaines and amido betaines, Contain fatty acid alkanolamides, polyglycol ether derivatives.

Anionic surfactants are preferably used in concentrations between 5% by weight and 20 wt .-% used. For example, Sodium Laureth Sulfate as it is under the Description Texapon N 70 is offered by Henkel or Disodium Laureth Sulfosuccinates as it is under the name Rewopol SBFA 30 from Witco is offered. Nonionic surfactants are preferably used in concentrations of 1 % By weight to 10% by weight. Examples are decyl glucoside as it is under the Description Oramix NS 10 from Seppic or Polysorbate 80 like it is offered under the name Tween 80 by ICI. Amphoteric surfactants are preferably used in concentrations of 1% by weight to 10 Wt .-% used. Examples are cocamidopropyl betaines such as Tego Betaine from Goldschmidt or Sodium Cocoamphoacetate as it is offered by Description Miranol Ultra is offered by Rhone Poulenc.

The percentages relate to the total weight of the preparations.

In addition, conditioning aids, especially water soluble conditioning agents, e.g. cationic conditioning agents, be included, e.g. in amounts of 0.001 to 10 wt .-%, based on the Total weight of the preparations. The preferred conditioning aids include polymeric quaternary compounds (quats). Polymer quats are widely used in Shampoos e.g. used with a concentration of 0.01 to 2 wt .-%. To belong to Polyquaternium-10 as it is known under the name Polymer JR 400 from Amerchol is offered or Hydroxypropyl Guar Hydroxypropyltrimonium Chloride as it is offered with the designation Jaguar C 162 by Rhone-Poulenc.

The preparations according to the invention can contain cosmetic auxiliaries, such as they are commonly used in such preparations, e.g. Preservatives, perfumes, anti-foaming substances, foam stabilizers, Dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moisturizing and / or moisturizing substances, lipid-replenishing agents, fats, oils, waxes, Alcohols, polyols and their toxicologically acceptable ethers and esters, branched and / or unbranched hydrocarbons, further antioxidants, stabilizers, pH regulators, Consistency agents, bactericides, deodorants, antimicrobial substances, Antistatic agents, UV absorbers, pearlescent agents, polymers, electrolytes, organic Solvents, silicone derivatives, plant extracts, vitamins and / or other active ingredients or other common components of a cosmetic or dermatological Formulation. Solution brokers, e.g. for incorporating hydrophobic components such as. of perfume preparations can be included.

The total amount of auxiliaries is, for example, 0.001 to 15% by weight, preferably 0.01 to 10 wt .-%, each based on the total weight of the Preparation.

The water content of the preparations is e.g. 20-99% by weight, preferably 50 to 95% by weight, in particular 55 to 90% by weight, in each case based on the total weight the preparation.

According to the invention, all of the other antioxidants for cosmetic and / or dermatological applications of suitable or customary antioxidants be used.

The total amount of the antioxidants is, for example, 0.001 to 2% by weight, preferably 0.01 to 1 wt .-%, each based on the total weight of the Preparation.

Other antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, Glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters ) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, homocysteine sulfoximine, buthioninsulfones, penta-, hexa -, Heptathioninsulfoximin) in very low tolerable doses (e.g. pmol to µmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid , Bile acid, bile extracts, bilirubin, biliverdin, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin e acetate), vitamin A and derivatives (vitamin-Apalmitat) and coniferyl benzoate of benzoin, rutinic acid and derivatives thereof, α-glycosyl rutin, ferulic acid, Furfurylidenglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, Nordihydroguajakharzsäure, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof , Mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives te (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

Preparations according to the invention can also advantageously contain substances absorb the UV radiation in the UV-B range, the total amount of Filter substances e.g. 0.001% by weight to 30% by weight, preferably 0.05 to 10% by weight, is in particular 0.1 to 1.0% by weight, based on the total weight of the preparations, to make available cosmetic preparations that the hair or the Protect skin from the entire range of ultraviolet radiation. You can also serve as a sunscreen for the hair or skin, especially the scalp.

• Salze der 2-Phenylbenzimidazol-5-sulfonsäure wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz, sowie die 2-Phenylbenzimidazol-5-sulfonsäure selbst;
• Sulfonsäure-Derivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihre Salze;
• Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und ihre Salze.

If the emulsions according to the invention contain UV-B filter substances, they can advantageously be water-soluble. Examples of advantageous water-soluble UV-B filters are:

• Salts of 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or triethanolammonium salt, and also 2-phenylbenzimidazole-5-sulfonic acid itself;
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
• Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their salts.

It can also be advantageous to add preparations according to the invention with UV-A filters offset that were previously usually contained in cosmetic preparations. It the quantities used for the UV-B combination can be used.

The weight ratio of the active ingredients oryzanol / calcium salts to each other in the Combinations can be varied in a wide range and can for example 100: 1 to 1: 100, preferably 10: 1 to 1:10, but also 1: 1.

The weight ratio of the active ingredients calcium salts / complexing agents to one another in the Combinations can be varied in a wide range and can for example 100: 1 to 1: 100, preferably 10: 1 to 1:10, but also 1: 1.

The preparations according to the invention can be prepared in the customary manner by mixing the individual components. The active ingredients of combinations according to the invention or the premixed components of the Combinations according to the invention can be added in the mixing process.

The pH of the preparations can be adjusted in a known manner by adding acids or bases, preferably by adding buffer mixtures, e.g. based on citric acid / citrate or phosphoric acid phosphate buffer mixtures. Preferably the pH is below 10, e.g. in the range of 4-8, especially in the Range from 5 - 7.

Unless otherwise stated, all quantities, proportions and percentages are on the weight and the total amount or on the total weight of the preparations or related to the respective mixture.

The following examples illustrate the invention.

The commercial product gamma-oryzanol is used as gamma-oryzanol in the examples Jan Dekker, DE, used.

The tetrasodium salt was used as the iminodisuccinic acid sodium salt.

The amounts in the examples are% by weight. Pearlescent conditioner shampoo 1 2 3 Polyquaternium-10 0.5 0.5 0.5 sodium laureth sulfate 9.0 9.0 9.0 cocoamidopropyl 2.5 2.5 2.5 pearlizing 2.0 2.0 2.0 Gamma-oryzanol 0.01 0.15 0.05 Calziumlactat 0,015 0.05 0.01 Disodium EDTA 0.1 0.2 0.15 Preservative, perfume, thickener, pH adjustment and solubilizer qs qs qs Water, VES (fully desalinated) ad 100.0 ad 100.0 ad 100.0 The pH is adjusted to 6. clear conditioner shampoo 4 5 6 Polyquaternium-10 0.5 0.5 0.5 sodium laureth sulfate 9.0 9.0 9.0 cocoamidopropyl 2.5 2.5 2.5 Gamma-oryzanol 0.25 0.2 0.15 calcium chloride 0,015 0.03 0.05 Iminodisuccinic acid, Na salt 0.2 0.3 0.8 Preservative, perfume, thickener, pH adjustment and solubilizer qs qs qs Water, VES ad 100.0 ad 100.0 ad 100.0 The pH is adjusted to 6. clear light shampoo with volume effect 7 8th 9 sodium laureth sulfate 10.0 10.0 10.0 cocoamidopropyl 2.5 2.5 2.5 Gamma-oryzanol 0.01 0.02 0.05 calcium chloride 0.01 0,008 0.05 Disodium EDTA 0.2 0.15 0.7 Preservative, perfume, thickener, pH adjustment and solubilizer qs qs qs Water, VES ad 100.0 ad 100.0 ad 100.0 The pH is adjusted to 5.5. clear conditioner shampoo 10 11 12 Polyquaternium-10 0.5 0.5 0.5 sodium laureth sulfate 9.0 9.0 9.0 cocoamidopropyl 2.5 2.5 2.5 Gamma-oryzanol 0.25 0.2 0.15 calcium chloride 0.0015 0,003 0.005 Preservative, perfume, thickener, pH adjustment and solubilizer qs qs qs Water, VES ad 100.0 ad 100.0 ad 100.0 The pH is adjusted to 6.

Claims (6)

Hair cosmetic cleaning agents that are different from the following preparations: (1): 2.5% by weight of octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight of calcium panthotenate, 39% by weight of absolute ethanol, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, (2): 2.5% by weight octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, 39% by weight absolute ethanol, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, (3): 8% by weight PVP / VA copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight calcium panthotenate, 39% by weight absolute ethanol, perfume, solubilizer, neutralizing agent / pH adjustment, Care substances qs, (4): 8% by weight PVP / VA copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, 39% by weight absolute ethanol, perfume, solubilizer, neutralizing agent / pH adjustment, Care substances qs, (5): 2.5% by weight octylacrylamides / acrylates / butylaminoethyl methacrylate copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, Ethanol abs. ad 100, (6): 2.5% by weight octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, Ethanol abs. ad 100, (7): 8% by weight PVP / VA copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, ethanol abs. ad 100, (8): 8% by weight PVP / VA copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, ethanol abs. ad 100, (9): Composition obtainable by combining according to Example 2 of DE1617557 of preparations A from 300 mg raffinoselauric acid ester, 30 mg orizanol, 10 mg lactotitanium complex compound, 50 mg cerebiosis, 100 ml water and B from 5 mg vitamin B6, 10 mg calcium pantothenate , 10 mg allantoin, 1 mg dihydro sodium acetoacetate, 10000 mg ethyl alcohol, 50 mg sodium arinate, 10 mg methyl paraoxybenzoate, in a suitable amount of perfume; and are characterized in that the preparations contain gamma-oryzanol and one or more calcium salts selected from the group formed by calcium panthotenate, calcium chloride and calcium lactate, the concentration of polyvalent metal cations present in free ion form being below 0.004 M. Use of active ingredient combinations and hair cosmetic cleaning compositions containing them, consisting of gamma-oryzanol and a calcium salt or more calcium salts, selected from the group formed by calcium panthotenate, calcium chloride and calcium lactate, the concentration of polyvalent metal cations present in free ion form being less than 0.004 M. , for the protection of hair cosmetic preparations and / or the scalp and / or the hair against undesired oxidation processes, the active substance combinations and hair cosmetic cleaning agents being different from the following preparations (according to EP 937450 A1 [(1) - (8)] and DE1617557 (9)} : (1): 2.5% by weight octylacrylamides / acrylates / butylaminoethyl methacrylate copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight calcium panthotenate, 39% by weight ethanol abs, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, (2): 2.5% by weight octylacrylamides / acrylates / butylaminoethyl methacrylate copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, 39% by weight ethanol abs, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, (3): 8% by weight PVP / VA copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight calcium panthotenate, 39% by weight ethanol abs, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, (4): 8% by weight PVP / VA copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, 39% by weight ethanol abs, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, (5): 2.5% by weight octylacrylamides / acrylates / butylaminoethyl methacrylate copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, Ethanol abs. ad 100, (6): 2.5% by weight octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, Ethanol abs. ad 100, (7): 8% by weight PVP / VA copolymer, 0.1% by weight, gamma-oryzanol, 0.05% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, ethanol abs. ad 100, (8): 8% by weight PVP / VA copolymer, 0.05% by weight, gamma-oryzanol, 0.08% by weight calcium panthotenate, perfume, solubilizer, neutralizing agent / pH adjustment, care substances qs, ethanol abs. ad 100, (9): Composition obtainable by combining according to Example 2 of DE1617557 of preparations A from 300 mg raffinoselauric acid ester, 30 mg orizanol, 10 mg lactotitanium complex compound, 50 mg cerebiosis, 100 ml water and B from 5 mg vitamin B6, 10 mg calcium pantothenate , 10 mg allantoin, 1 mg dihydro sodium acetoacetate, 10000 mg ethyl alcohol, 50 mg sodium arinate, 10 mg methyl paraoxybenzoate, in a suitable amount of perfume. Agents or use according to Claim 1 or 2, characterized in that they contain 0.02 to 2.00% by weight of one or more complexing agents, preferably 0.05 to 1.0% by weight, in each case based on the total weight of the agents , contain. Agents or use according to Claim 1, 2 or 3, characterized in that they contain 0.001 to 5.0% by weight of gamma-oryzanol, preferably 0.01 to 2.0% by weight, in each case based on the total weight of the agents, contain. Agent or use according to one of the preceding claims, characterized in that additional surfactants and / or cosmetic or dermatological auxiliaries, additives and / or active ingredients are additionally contained. Agents or use according to one of the preceding claims, characterized in that they contain 0.001 to 0.05% by weight of one or more calcium salts, preferably 0.02 to 0.05% by weight, in each case based on the total weight of the agents ,